Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols.

Desulfurization of organosulfur compounds is a highly important reaction because of its relevance to the hydrodesulfurization (HDS) process of fossil fuels. A reaction system involving Co(BF4 )2 ·6H2 O and the dinucleating ligands HBPMP or HPhBIMP has been developed that could desulfurize a large number of thiophenes, sulfides, and thiols to generate the complexes [Co2 (BPMP)(μ2 -SH)(MeCN)](BF4 )2 (1a), [Co2 (BPMP)(SH)2 ](BF4 ) (1b), and [Co2 (PhBIMP)(μ2 -SH)(X)](BF4 )2 [X = DMF (2a), MeCN (2c)], while the substrates are mostly converted to the corresponding alcohols/phenols. This convenient desulfurization process has been demonstrated for 25 substrates in 6 different solvents at room temperature.